JPS59166965A - Toner for developing electrostatic latent image - Google Patents

Abstract

PURPOSE:To prevent the contamination of a PVC product and the staining of a duplicated image by using a compd. selected from a methacrylic acid, acrylic acid and their esters having a specific glass transition point. CONSTITUTION:A toner is costituted of a polymer A incorporated therein with one kind of compd. (a) selected from the group consisting of hydroxyalkyl methacrylate, hydroxy alkyl acrylate, acrylic acid, methacrylic acid, glycidyl methacrylate, glycidyl acrylate, methacrylonitrile, and acrylonitrile as a constituting component and a coloring agent B. The component A is the polymer in which 30-70wt% a styrene monomer or methyl methacrylate or both thereof and 10-30wt% one kind among alkyl methacrylate, alkyl acrylate, vinyl ester or vinyl ether are incorporated in addition to said compd. (a) at such a rate to make 100wt% total quantity. Such polymer has good thermal fixability and stability against moisture without sticking of vinyl chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a toner for developing electrostatic images used in electrophotography, electrostatic recording, etc. More specifically, in this field, objects manufactured from vinyl chloride polymers containing plasticizers, etc. (for example, document cases made of plasticized vinyl chloride polymers, electrical cords coated with the polymers, etc.) On the other hand, it is resistant to adhesion.

The present invention relates to a toner for developing electrostatic images with excellent migration resistance, stain resistance, etc.

Conventionally, toners for developing electrostatic images used in electrophotography, electrostatic recording, etc. contain 9 colorants, charge control agents, bisphenol A type epoxy resin, polystyrene, styrene-butyl methacrylate copolymer, and styrene-butyl acrylate copolymer. The toner itself is composed of a binder resin such as a polymer.

Alternatively, a copy image obtained by electrophotography, electrostatic recording, etc. using such toner may adhere to or transfer to an object made of a vinyl chloride polymer plasticized with dioctyl phthalate, dibutyl phthalate, or the like.

As a result, the object becomes contaminated. This method had serious drawbacks such as smearing of the copied image.

The present invention solves these problems.

In other words, one aspect of the present invention is.

Glass transition point is 50-80'C.

Hydroxyalkyl methacrylate, hydroxyalkyl acrylate, methacrylic acid, acrylic acid.

Glycidyl methacrylate, glycidyl acrylate.

An electrostatic charge comprising a polymer (I) containing 20 to 50 weight by weight of at least one compound (a) selected from the group consisting of methacrylonitrile and acrylonitrile, and a colorant (II). This invention relates to toner for image development.

The polymer CI+ of the present invention has a glass transition temperature of 50 to 80
Must be within ℃ range. If the temperature is less than 50°C, the adhesion of the toner to vinyl chloride polymer containing plasticizer cannot be reduced, especially at high temperatures, and if it exceeds 80°C, the adhesion can be reduced, but the heat fixing inferior in sex.

Further, the polymer (1) of the present invention has 20 to 50% by weight of the above-mentioned component (a) as a constituent component. (
If the component a) is less than 20% by weight, it will not be possible to reduce the adhesion of the toner to the vinyl chloride polymer containing a plasticizer, and if it exceeds 50% by weight, the adhesion of the toner can be reduced, but the moisture resistance will be reduced. Less stable.

Hydroxyalkyl methacrylates that can be used as component (a) include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and hydroxybutyl methacrylate.

Also, as hydroxyalkyl acrylate.

2-hydroxyethyl acrylate, acrylic acid 2t:
Examples include l-'a-hydroxypropyl, acryl, and the like.

The constituent components other than the above component (a) of the polymer (1) are appropriately selected and used so that the glass transition point of the 9 polymer (Il is 50 to 80'C).

The constituent components include methyl methacrylate, styrene,
ατ methylstyrene, p-methylstyrene, 0-methylstyrene, I'll-methylstyrene.

Styrenic monomers such as p-tert-butylstyrene and p-chlorostyrene, and ethyl methacrylate.

n-propyl methacrylate, inglovir methacrylate, n-butyl methacrylate, isofutan methacrylate,
eth-butyl methacrylate, n-pentyl methacrylate,
Isopentyl methacrylate.

Neopentyl methacrylate, 2-methylbutyl methacrylate, n-hexyl methacrylate or its isomers, n-octyl methacrylate or its isomers, n-nonyl methacrylate or its isomers, n-octyl methacrylate or its isomers an alkyl methacrylate having an alkyl group having 2 to 12 carbon atoms, such as n-dodecyl methacrylate or an isomer thereof.

Similar alkyl acrylates, alkyl acrylates having an alkyl group having 1 to 12 carbon atoms such as methyl acrylate,
Examples include vinyl alcohol esters (vinyl esters) such as vinyl acetate and vinyl propionate, and vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl n-butyl ether.

Polymer (I) contains 20 to 50% by weight of component (a) and 30 to 70% of methyl methacrylate and/or styrene monomer as component (b) in order to have a glass transition point of 50 to 80°C. As a weight factor and component (C).

At least one compound selected from the group consisting of alkyl methacrylates having an alkyl group having 2 to 12 carbon atoms, alkyl acrylates having an alkyl group having 1 to 12 carbon atoms, vinyl esters, and vinyl ethers 10 to 300
Preferably, the amount is 30% by weight and 10,000 parts by weight. The combination of the above-mentioned components (b) and (C) as components other than component (a) lowers the glass transition point to 50%.
It is easy to adjust the glass transition point to 50 to 80°C, and it may be difficult to adjust the glass transition point to 50 to 80°C if the amounts of components (b) and (C) are outside the above range. be. It is recommended to use methyl methacrylate and/or styrene as component (b) and use butyl methacrylate and/or butyl acrylate as component (C) to adjust the glass transition point to 50 to 80°C. most preferred.

To produce the polymer (Il), the raw materials for component (a) and other components are mixed with benzoyl peroxide, azobisisobutyro, etc. by any method such as solution polymerization, suspension polymerization, emulsion polymerization, or bulk polymerization. Copolymerize using a polymerization initiator such as nitrile.

Copolymer CI) may be a terpolymer of component (a), component (b), and component (C), or may be a terpolymer of component (a), component (C),
A blend of any homopolymer, binary copolymer, or terpolymer of component (b) and component (C) may be used. However, the proportions of component (a), component (b), and component (C) are as described above.

Note that the glass transition temperature is determined by thermo-mechanical analysis penetration.
nical analysis penetration
n) load 701. Measurements were made at a temperature increase rate of 10° C./min. A device that can be used for this measurement is commercially available as TMS-1 from PerkinElmer.

The coloring agent of the present invention (formerly, any conventionally known coloring agent can be used; for example, carbon black, rhodamine 6G
Examples include ferric chloride, phthalocyanine blue, phthalocyanine green, watching red strontium, watching red strontium, triiron tetroxide, and sesquiferric oxide. Colorant (formerly 0 for polymer (1))
．． It is appropriately selected and used within the range of 1 to 60% by weight.

If necessary, dyes and/or pigments for charge control, or dyes and/or pigments for colors complementary to the colorant may be appropriately selected and added to the toner for developing electrostatic images of the present invention. Examples of dyes and pigments include alcohol soluble nigrosine dyes, fatty acid-modified nigrosine dyes, triphenylmethane dyes, chromium complexes of monoazo dyes, cobalt complexes of monoazo dyes, and chromium complexes of salicylic acid. These are 1 for polymer (I)
It is preferable to use it in an amount of 0% by weight or less.

In order to expect the effect of adding it, it is preferable to use it in an amount of 0.5% by weight or more.

The toner for developing an electrostatic image according to the present invention may include silicon dioxide, zinc stearate, polytetrafluoroethylene, silicone oil, etc., as examples of necessary machining.

Any conventionally known developing method can be applied to the toner for developing an electrostatic image according to the present invention. For example, it can be dispersed in an alkane or the like and subjected to wet development, or it can be combined with suitable iron oxide powder, glass beads, etc. to perform magnetic brush development or cascade development. Furthermore, it is also possible to blend a magnetic material into the electrostatic charge image developing toner of the present invention and develop the toner as a magnetic toner by a magnetic brush method or the like.

Furthermore, the toner for developing an electrostatic image according to the present invention is as follows.

If necessary, reversal development can be performed in addition to regular development.

The toner for developing electrostatic images according to the present invention can be produced by melt-mixing Jugetsuji and a colorant at an appropriate temperature, cooling, and then crushing and classifying the mixture into desired particle sizes.

Alternatively, the resin and colorant can be dispersed in a suitable solvent and then spray-dried. That is 9
The toner for electrostatic image development according to the present invention can be produced using any conventionally known technique.

Next, examples of the present invention will be shown.

Example 1 55 parts by weight of styrene, 15 parts by weight of n-phytyl methacrylate, 30 m parts of β-hydroxyethyl methacrylate, and 1 polymer of penzoyl oxide were dissolved in toluene and copolymerized by solution polymerization to form a glass. A copolymer f having a transition temperature of 70°C was obtained.

85 parts by weight of this copolymer, 10 parts by weight of carbon black and fatty acid-modified nigrosine dye (oil black BY,
5 parts by weight (trade name, manufactured by Orient Chemical Industry Co., Ltd.) were mixed together and then melted and kneaded. After cooling, the mixture was coarsely pulverized with a hammer mill, further finely pulverized with an air-jet type pulverizer, and classified to obtain a toner having a particle size of 5 to 30 μm.

5 parts by weight of the above toner and iron oxide powder carrier (mainly particle size 20
0 to 300, :l, 95 parts by weight of EFV200/300゜Japanese Iron Powder (trade name) are combined to make a developer, and a Sharp dry electronic copying machine SF~750 (Sharp ■trade name) is used to make paper. The image was created. As a result, a good image with high image density and no fog was obtained.

The paper on which the above image had been formed was sandwiched between plasticized vinyl chloride resin sheets (containing 25% by weight of the plasticizer dioctyl phthalate) and left at 50° C. for 50 hours to examine the adhesion of the image to the sheet. As a result, it was found that 9 images did not adhere to the sheet at all.

The above toner was brought into contact with a plasticized vinyl chloride resin-coated electrical cord, and left at 50° C. for 50 hours to examine the adhesion of the toner to the cord. As a result, it was found that toner did not adhere to the cord at all.

Example 2 40 parts by weight of styrene, 10 parts by weight of methyl methacrylate,
5 parts by weight of n-butyl acrylate, 20 parts by weight of n-butyl methacrylate, and 2 parts by weight of β-hydroxyethyl acrylate.
A copolymer having a glass transition temperature of 55° C. was obtained in the same manner as in Example 1 using 5 parts by weight. A toner having a particle size of 5 to 30 μn was prepared in the same manner as in Example 1 using 95 parts by weight of this copolymer and 5 parts by weight of carbon black.

Using the above toner, a developer was obtained in the same manner as in Example 1, and an image was formed on paper using a Selex 900 copying machine (trade name: Copia ■). the result.

Good images with high image density and no fog were obtained.

The paper on which the image was formed was sandwiched between plasticized vinyl chloride resin sheets (containing 25% by weight of plasticizer dioctyl phthalate) and left at 50° C. for 50 hours to examine the adhesion of the image to sorting. As a result, it was found that one image did not adhere to the sheet at all.

The above toner was brought into contact with a plasticized vinyl chloride resin-coated electrical cord, and left at 50° C. for 50 hours to examine the adhesion of the toner to the cord. As a result, it was found that toner did not adhere to the cord at all.

Example 3 A copolymer with a glass transition temperature of 60° C. was obtained in the same manner as in Examples 1 and 7 using 55 parts by weight of styrene, 15 parts by weight of n-butyl methacrylate, and 30 parts by weight of 2-hydroxypropyl methacrylate. . A toner and a developer were prepared in exactly the same manner as in Example 1 except that this copolymer was used.
Image formation was performed to obtain a good image with no fog and high image density.

Still, in the same manner as in Example 1, the adhesion of the above image to the vinyl chloride resin sheet and the adhesion to the cord were examined. As a result, no toner adhered to the sheet or cord.

Examples 4 to 9 and Comparative Examples 1 to 6 Copolymers were obtained in the same manner as in Example 1 using the formulations shown in Table 1. Table 1 shows the glass transition temperature of each copolymer.

Using the obtained copolymer, Examples 4.6 and 8 and Comparative Examples 1, 2 and 6 were prepared according to Example 1, Examples 5.7 and 9 and Comparative Examples 3, 4 and 5. A developer was prepared according to Example 2, and the adhesion of the toner to the vinyl chloride sheet and the adhesion to the vinyl chloride cord were examined. These results are shown in Table 1. The evaluation is as follows.

(1) Adhesion to sheet: ○: No adhesion at all.

×...Tone corresponding to the image -Adherence.

(2) Adhesion to cord 20: No adhesion at all.

×...Toner may adhere to the The board becomes dark and sticky. Show your gender.

As is clear from the above, the electrostatic (T) image developing toner according to the present invention (2) is made of vinyl chloride containing a plasticizer (2).
■Excellent J adhesion.

Agent: Patent Attorney Kunihiko Wakabayashi

Claims (1)

[Claims] 1. A glass transition point of 50 to 80°C, consisting of hydroxyalkyl methacrylate, hydroxyalkyl acrylate, methacrylic acid, acrylic acid, glycidyl methacrylate, glycidyl acrylate, methacrylonitrile, and acrylonitrile. A toner for developing an electrostatic image, comprising at least one compound selected from the group consisting of a polymer (1) containing 20 to 50% by weight as an ark component, and a colorant (n).2 Polymer ( 11 as a constituent component. The above (a) component has 20 to 50% carbon dioxide. (b) 30 to 70% by weight of styrenic monomer and/or methyl methacrylate and (C1 alkyl group having 2 to 12 carbon atoms) At least one compound selected from the group consisting of alkyl acrylates, vinyl esters, and vinyl ethers having a radical having
The toner for developing an electrostatic image according to claim 2, which is a polymer comprising 0 to 30 parts by weight in a proportion such that the total part by weight is 100 parts by weight. 3. Component (b) is styrene and/or methyl methacrylate, and component (C) is butyl methacrylate and/or
or butyl acrylate, the toner for developing an electrostatic image according to claim 2.